High porosity fluorided silica-coated alumina activator-supports and uses thereof in metallocene-based catalyst systems for olefin polymerization

ABSTRACT

Fluorided silica-coated alumina activator-supports have a bulk density from 0.15 to g/mL, a total pore volume from 0.85 to 2 mL/g, a BET surface area from 200 to 500 m2/g, an average pore diameter from 10 to 25 nm, and from 80 to 99% of pore volume in pores with diameters of greater than 6 nm. Methods of making the fluorided silica-coated alumina activator-supports and using the fluorided silica-coated aluminas in catalyst compositions and olefin polymerization processes also are described. Representative ethylene-based polymers produced using the compositions and processes have a melt index of 0.1 to 10 g/10 min and a density of 0.91 to 0.96 g/cm3, and contain from 70 to 270 ppm solid oxide and from 2 to 18 ppm fluorine.

REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 63/348,044, filed on Jun. 2, 2022, the disclosure ofwhich is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present disclosure generally relates to fluorided solid oxideactivator-supports, methods for making the activator-supports,metallocene-based catalyst compositions containing theactivator-supports, methods for using the catalyst compositions topolymerize olefins, and the polymer resins produced using such catalystcompositions. More particularly, the present disclosure relates tofluorided silica-coated alumina activator-supports with higher porevolume and porosity, and having average pore diameters greater than 10nm in diameter.

BACKGROUND OF THE INVENTION

It would be beneficial to produce solid activator-supports that haveincreased catalytic activity in olefin polymerization processes, forexample, using metallocene-based catalyst systems for the production ofethylene-based polymers. An increase in catalytic activity of the solidactivator-support results in a reduction in the amount of themetallocene component required in the catalyst system, which cantranslate to significant cost savings. Accordingly, it is to these endsthat the present invention is generally directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

Aspects of this invention are directed to fluorided silica-coatedalumina activator-supports. For instance, in one aspect, the fluoridedsilica-coated alumina can have (or can be characterized by) a bulkdensity from 0.15 to 0.37 g/mL, a total pore volume from 0.85 to 2 mL/g,a BET surface area from 200 to 500 m²/g, and an average pore diameterfrom 10 to 25 nm. In another aspect, the fluorided silica-coated aluminacan have (or can be characterized by) a bulk density from 0.15 to 0.37g/mL, a total pore volume from 0.85 to 2 mL/g, a BET surface area from200 to 500 m²/g, and from 80 to 99% of pore volume of the fluoridedsilica-coated alumina in pores with diameters of greater than 6 nm.

Catalyst compositions also are provided herein, and such catalystcompositions can comprise a metallocene compound, any of the fluoridedsilica-coated alumina activator-supports disclosed herein, and anoptional co-catalyst. Olefin polymerization processes also areencompassed, and such processes can comprise contacting any of thecatalyst compositions provided herein with an olefin monomer and anoptional olefin comonomer in a polymerization reactor system underpolymerization conditions to produce an olefin polymer.

Another aspect of the invention is a process to produce a fluoridedsilica-coated alumina, and in this aspect, the process can comprisecontacting a fluoriding agent with a silica-coated alumina to producethe fluorided silica-coated alumina. The silica-coated alumina can have(or can be characterized by) a bulk density from 0.15 to 0.37 g/mL, atotal pore volume from 1.1 to 2.5 mL/g, a BET surface area from 250 to600 m²/g, and an average pore diameter from 10 to 25 nm.

In yet another aspect, supported metallocene catalysts are provided andsuch catalysts can comprise a metallocene compound and a fluoridedsilica-coated alumina. The amount of the metallocene compound adsorbedper gram of the fluorided silica-coated alumina can be at least 55μmol/g (such as from 60 to 130 μmol/g) and/or the number of molecules ofthe metallocene compound adsorbed per nm² of surface area of thefluorided silica-coated alumina can be at least 0.1 molecules per nm²(such as from 0.1 to 0.3 molecules per nm²).

Other aspects of this invention are directed to ethylene polymers (whichare typically in the form of pellets or beads) characterized by a meltindex (MI) in a range from 0.1 to 10 g/10 min and a density in a rangefrom 0.91 to 0.96 g/cm³. These ethylene polymers can contain from 70 to270 ppm solid oxide (e.g., silica-coated alumina) and from 2 to 18 ppmfluorine. Further, such ethylene polymers also can contain from 0.5 to 5ppm of zirconium or hafnium.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects may bedirected to various feature combinations and sub-combinations describedin the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents plots of the pore volume distributions as a function ofpore diameter (nm) for the silica-coated aluminas of Comparative Example1 (CE-1) and Inventive Example 1 (IE-1).

FIG. 2 presents plots of the surface area distributions as a function ofpore diameter (nm) for the silica-coated aluminas of CE-1 and IE-1.

FIG. 3 presents plots of the pore volume distributions as a function ofpore diameter (nm) for the fluorided silica-coated aluminas ofComparative Example 2 (CE-2) and Inventive Example 2 (IE-2).

FIG. 4 presents plots of the surface area distributions as a function ofpore diameter (nm) for the fluorided silica-coated aluminas of CE-2 andIE-2.

FIG. 5 presents a plot of the particle size distributions of thefluorided silica-coated aluminas of CE-2 and IE-2.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Herein, features of the subject matter are described such that, withinparticular aspects, a combination of different features can beenvisioned. For each and every aspect and each and every featuredisclosed herein, all combinations that do not detrimentally affect thecompounds, compositions, processes, or methods described herein arecontemplated with or without explicit description of the particularcombination. Additionally, unless explicitly recited otherwise, anyaspect or feature disclosed herein can be combined to describe inventivecompounds, compositions, processes, or methods consistent with thepresent disclosure.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

While compositions and methods/processes are described herein in termsof “comprising” various components or steps, the compositions andmethods/processes also can “consist essentially of” or “consist of” thevarious components or steps, unless stated otherwise. For example, acatalyst composition consistent with aspects of the present inventioncan comprise; alternatively, can consist essentially of; oralternatively, can consist of; a metallocene compound, a fluoridedsilica-coated alumina, and a co-catalyst.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “a metallocene compound” or “a comonomer” ismeant to encompass one, or mixtures or combinations of more than one,metallocene compound or comonomer, respectively, unless otherwisespecified.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Unless otherwise specified, “substituted” is intended to be non-limitingand include inorganic substituents or organic substituents as understoodby one of ordinary skill in the art.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and the like, as well as alloysand blends thereof. The term “polymer” also includes impact, block,graft, random, and alternating copolymers. A copolymer is derived froman olefin monomer and one olefin comonomer, while a terpolymer isderived from an olefin monomer and two olefin comonomers. Accordingly,“polymer” encompasses copolymers and terpolymers derived from any olefinmonomer and comonomer(s) disclosed herein. Similarly, the scope of theterm “polymerization” includes homopolymerization, copolymerization, andterpolymerization. Therefore, an ethylene polymer includes ethylenehomopolymers, ethylene copolymers (e.g., ethylene/α-olefin copolymers),ethylene terpolymers, and the like, as well as blends or mixturesthereof. Thus, an ethylene polymer encompasses polymers often referredto in the art as LLDPE (linear low density polyethylene) and HDPE (highdensity polyethylene). As an example, an olefin copolymer, such as anethylene copolymer, can be derived from ethylene and a comonomer, suchas 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer wereethylene and 1-hexene, respectively, the resulting polymer can becategorized an as ethylene/1-hexene copolymer. The term “polymer” alsoincludes all possible geometrical configurations, unless statedotherwise, and such configurations can include isotactic, syndiotactic,and random symmetries. Moreover, unless stated otherwise, the term“polymer” also is meant to include all molecular weight polymers.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, that can constitute one component of a catalyst composition, whenused, for example, in addition to a fluorided silica-coated alumina. Theterm “co-catalyst” is used regardless of the actual function of thecompound or any chemical mechanism by which the compound may operate.

The term “metallocene” as used herein describes compounds comprising atleast one η³ to η⁵-cycloalkadienyl-type moiety, wherein η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands can include H, therefore this inventioncomprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like. In some contexts, themetallocene is referred to simply as the “catalyst,” in much the sameway the term “co-catalyst” is used herein to refer to, for example, anorganoaluminum compound.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of thedisclosed or claimed catalyst composition/mixture/system, the nature ofthe active catalytic site, or the fate of the co-catalyst, themetallocene compound, or the fluorided silica-coated alumina, aftercombining these components. Therefore, the terms “catalyst composition,”“catalyst mixture,” “catalyst system,” and the like, encompass theinitial starting components of the composition, as well as whateverproduct(s) may result from contacting these initial starting components,and this is inclusive of both heterogeneous and homogenous catalystsystems or compositions. The terms “catalyst composition,” “catalystmixture,” “catalyst system,” and the like, can be used interchangeablythroughout this disclosure.

The terms “contacting” and “combining” are used herein to describecompositions, processes, and methods in which the materials orcomponents are contacted or combined together in any order, in anymanner, and for any length of time, unless otherwise specified. Forexample, the materials or components can be blended, mixed, slurried,dissolved, reacted, treated, compounded, or otherwise contacted orcombined in some other manner or by any suitable method or technique.

Several types of ranges are disclosed in the present invention. When arange of any type is disclosed or claimed, the intent is to disclose orclaim individually each possible number that such a range couldreasonably encompass, including end points of the range as well as anysub-ranges and combinations of sub-ranges encompassed therein. As arepresentative example, the total pore volume of a fluoridedsilica-coated alumina can be in certain ranges in various aspects ofthis invention. By a disclosure that the pore volume can be in a rangefrom 0.85 to 2 mL/g, the intent is to recite that the pore volume can beany amount in the range and, for example, can include any range orcombination of ranges from to 2 mL/g, such as from 0.85 to 1.6 mL/g,from 0.9 to 1.8 mL/g, from 0.9 to 1.5 mL/g, or from 1 to 1.7 mL/g, andso forth. Likewise, all other ranges disclosed herein should beinterpreted in a manner similar to this example.

In general, an amount, size, formulation, parameter, range, or otherquantity or characteristic is “about” or “approximate” whether or notexpressly stated to be such. Whether or not modified by the term “about”or “approximately,” the claims include equivalents to the quantities orcharacteristics.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices, and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference in their entirety for the purpose of describing anddisclosing, for example, the constructs and methodologies that aredescribed in the publications and patents, which might be used inconnection with the presently described invention.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein are processes for preparing fluorided silica-coatedaluminas and metallocene-based catalyst compositions containing thefluorided silica-coated aluminas. Polymerization processes using themetallocene-based catalyst compositions to produce olefin polymers alsoare provided.

Beneficially, the fluorided silica-alumina activator-supports have highpore volume and increased porosity, as well as higher adsorptivity formetallocene compounds, enabling significant increases in catalyticactivity.

Fluorided Silica-Coated Alumina Activator-Supports

A fluorided silica-coated alumina activator-support encompassed hereincan have (or can be characterized by) a bulk density from 0.15 to 0.37g/mL, a total pore volume from 0.85 to 2 mL/g, a BET surface area from200 to 500 m²/g, and an average pore diameter from 10 to 25 nm. Anotherfluorided silica-coated alumina encompassed herein can have (or can becharacterized by) a bulk density from 0.15 to 0.37 g/mL, a total porevolume from to 2 mL/g, a BET surface area from 200 to 500 m²/g, and from80 to 99% of pore volume of the fluorided silica-coated alumina in poreswith diameters of greater than 6 nm. These illustrative and non-limitingexamples of fluorided silica-coated alumina activator-supportsconsistent with the present invention also can have any of theproperties listed below and in any combination, unless indicatedotherwise.

Generally, the fluorided silica-coated alumina can have a bulk densityfrom 0.15 to g/mL. Other representative and non-limiting ranges for thebulk density include from 0.15 to 0.32 g/mL, from 0.17 to 0.3 g/mL, from0.18 to 0.28 g/mL, or from 0.18 to 0.25 g/mL, and the like. The totalpore volume of the fluorided silica-coated alumina can range from 0.85to 2 mL/g, while the BET surface area can range from 200 to 500 m²/g. Insome aspects, the total pore volume can range from 0.85 to 1.6 mL/g;alternatively, from 0.9 to 1.8 mL/g; alternatively, from 0.9 to 1.5mL/g; or alternatively, from 1 to 1.7 mL/g. Likewise, the BET surfacearea, in some aspects, can range from 250 to 450 m²/g; alternatively,from 200 to 425 m²/g; or alternatively, from 270 to 425 m²/g.

Beneficially, the fluorided silica-coated alumina activator-support hasa significant amount of meso-pores (pores with a pore size greater thanor equal to 10 nm in diameter). One test to quantify the significantamount of larger pores is the average pore diameter in nanometers(4000*PV/SA, with PV in mL/g and SA in m²/g). For example, a fluoridedsilica-coated alumina with a total pore volume of 0.96 mL/g and a totalBET surface area of 330 m²/g translates to an average pore diameter of11.6 nm. While not limited thereto, the fluorided silica-coated aluminadisclosed herein can have an average pore diameter from 10 to 20 nm inone aspect, from 10.5 to 22 nm in another aspect, from 11 to 22 nm inyet another aspect, and from 11 to 19 nm in still another aspect.

Another indicator of the significant amount of larger pores is thepercentage of the pore volume in pores with diameters of greater than 6nm. The fluorided silica-coated alumina can have, for instance, from 80to 97%, from 82 to 99%, from 82 to 97%, from 83 to 98%, or from 84 to99%, of the pore volume in pores with diameters of greater than 6 nm.

Another indicator of the amount of larger pores of the fluoridedsilica-coated alumina is a significant amount of the pore volume inpores with diameters of greater than 20 nm and/or greater than 40 nm. Inone aspect, the amount of the pore volume in pores with diameters ofgreater than 20 nm can fall within a range from 9.5 to 30%, from 10 to30%, from 10 to 27%, from 10.5 to 28%, or from 11 to 26%, while notbeing limited thereto. Additionally or alternatively, the fluoridedsilica-coated alumina can be characterized as having from 3.5 to 15%,from 3.5 to 13%, from 4 to 15%, from 4 to 13%, or from 5 to 15%, of thepore volume in pores with diameters of greater than 40 nm.

Another indicator of the significant amount of larger pores is theamount of pore volume present in pores with diameters of greater than 6nm. While not being limited thereto, the fluorided silica-coated aluminacan have a pore volume of pores with diameters of greater than 6 nm ofat least 0.7 mL/g, at least 0.8 mL/g, or at least 0.85 mL/g, withrepresentative ranges including from 0.7 to 1.6 mL/g, from 0.7 to 1.4mL/g, from 0.75 to 1.5 mL/g, from 0.8 to 1.6 mL/g, or from 0.8 to 1.4mL/g, and the like. Similarly, the fluorided silica-coated alumina canhave a pore volume of pores with diameters of greater than 20 nm of atleast 0.09 mL/g or at least 0.1 mL/g, with representative rangesincluding from 0.09 to mL/g, from 0.09 to 0.34 mL/g, from 0.1 to 0.4mL/g, from 0.1 to 0.36 mL/g, or from to 0.34 mL/g, and the like.

Referring now to characterizations of the fluorided silica-coatedalumina based on surface area, a vast majority of surface area residesin pores with diameters of greater than 6 nm. While not limited thereto,the fluorided silica-coated alumina can have from 65 to 98%, from 65 to94%, from 65 to 91%, from 68 to 94%, from 70 to 98%, or from 70 to 91%,of surface area in pores with diameters of greater than 6 nm.Additionally or alternatively, the fluorided silica-coated alumina canbe characterized as having from 19.5 to 55%, from to 55%, from 20 to50%, from 21 to 55%, or from 21 to 50%, of the surface area in poreswith diameters of greater than 10 nm, although not necessarily limitedthereto.

Another indicator of the larger amount of surface area residing inlarger pores is the amount of surface area of the fluoridedsilica-coated alumina in pores having diameters of greater than 6 nm.While not being limited thereto, the fluorided silica-coated alumina canhave a surface area of pores with diameters of greater than 6 nm of atleast 250 m²/g or at least 275 m²/g, with representative rangesincluding from 250 to 475 m²/g, or from 275 to 450 m²/g, and the like.Similarly, the fluorided silica-coated alumina can have a surface areaof pores with diameters of greater than 10 nm range of at least 78 m²/gor at least 85 m²/g, with representative ranges including from 78 to 200m²/g, or from 85 to 180 m²/g, and the like.

The fluorided silica-coated alumina can have any suitable particle size,as would be recognized by those of skill in the art. Illustrative andnon-limiting ranges for the average (d50) particle size of the fluoridedsilica-coated alumina can include from 30 to 150 microns, from 40 to 100microns, or from 45 to 85 microns, and the like.

The silica content of the fluorided silica-coated alumina, while notbeing necessarily limited to, often ranges from 10 to 80 wt. %, based onthe weight of the silica-coated alumina. More often, the fluoridedsilica-coated alumina contains from 20 to 60 wt. % silica in one aspect,from 25 to 55 wt. % silica in another aspect, and from 35 to 45 wt. %silica in yet another aspect. These percentages are based on the weightof silica-coated alumina.

Likewise, while not being limited thereto, the fluorided silica-coatedalumina can contain from 0.5 to 18 wt. % F, although any suitable amountcase be used. In many instances, the fluorided silica-coated aluminadescribed herein contains from 1 to 13 wt. % F, from 2 to 9 wt. % F,from 3 to 16 wt. % F, or from 3 to 10 wt. % F, and the like. Theseweight percentages are based on the weight of the fluoridedsilica-coated alumina.

Catalyst Compositions

The present invention encompasses catalyst compositions comprising ametallocene compound and a fluorided silica-coated aluminaactivator-support. These catalyst compositions can be utilized toproduce polyolefins—homopolymers, copolymers, and the like—for a varietyof end-use applications. In aspects of the present invention, it iscontemplated that the catalyst composition can contain one metallocenecompound (or two or more metallocene compounds). Further, more than onefluorided silica-coated alumina also can be utilized. As a skilledartisan would readily recognize, supporting the metallocene compound(s)on the fluorided silica-coated alumina would not impact the overall porevolume and surface area, the pore volume distribution, and the surfacearea distribution, thus these features of a supported metallocenecatalyst would be effectively the same as those disclosed hereinabovefor the fluorided silica-coated alumina (based on the amount ofmetallocene adsorbed, as illustrated in the example section thatfollows).

A supported metallocene catalyst in one aspect of this invention cancomprise a metallocene compound and a fluorided silica-coated alumina,and the amount of the metallocene compound adsorbed per gram of thefluorided silica-coated alumina can be at least 55 μmol/g or at least 60μmol/g, with representative ranges including from 55 to 155 μmol/g, from60 to at least 130 μmol/g, and the like. A supported metallocenecatalyst in another aspect of this invention can comprise a metallocenecompound and a fluorided silica-coated alumina, and the number ofmolecules of the metallocene compound adsorbed per nm² of surface areaof the fluorided silica-coated alumina can be at least 0.1 molecules pernm² or at least 0.12 molecules per nm², with representative rangesinclude from 0.1 to 0.3 molecules per nm², from 0.1 to 0.24 moleculesper nm², or from 0.12 to 0.22 molecules per nm², and the like.

Catalyst compositions of the present invention comprise a metallocenecompound and a fluorided silica-coated alumina, and optionally, suchcatalyst compositions can further comprise one or more than oneco-catalyst compound or compounds (suitable co-catalysts, such asorganoaluminum compounds, are discussed herein). Thus, a catalystcomposition of this invention can comprise a metallocene compound, afluorided silica-coated alumina, and an organoaluminum compound.Accordingly, a catalyst composition consistent with aspects of theinvention can comprise (or consist essentially of, or consist of) ametallocene compound, a fluorided silica-coated alumina, and anorganoaluminum compound.

In another aspect of the present invention, a catalyst composition isprovided which comprises a metallocene compound, a fluoridedsilica-coated alumina, and an organoaluminum compound, wherein thiscatalyst composition is substantially free of aluminoxanes, organoboronor organoborate compounds, ionizing ionic compounds, or combinationsthereof; alternatively, substantially free of aluminoxanes;alternatively, substantially free or organoboron or organoboratecompounds; or alternatively, substantially free of ionizing ioniccompounds. For instance, the catalyst composition can contain less than500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm,independently, of aluminoxanes, organoboron or organoborate compounds,and ionizing ionic compounds. In these aspects, the catalyst compositionhas catalyst activity, discussed below, in the absence of theseadditional materials. For example, a catalyst composition of the presentinvention can consist essentially of a metallocene compound, a fluoridedsilica-coated alumina, and an organoaluminum compound, wherein no othermaterials are present in the catalyst composition which wouldincrease/decrease the activity of the catalyst composition by more thanabout 10% from the catalyst activity of the catalyst composition in theabsence of said materials.

However, in other aspects of this invention, these co-catalysts can beemployed. For example, a catalyst composition comprising a metallocenecomplex and a fluorided silica-coated alumina can further comprise aco-catalyst. Suitable co-catalysts in this aspect can include, but arenot limited to, aluminoxane compounds, organoboron or organoboratecompounds, ionizing ionic compounds, organoaluminum compounds,organozinc compounds, organomagnesium compounds, organolithiumcompounds, and the like, or any combination thereof; or alternatively,organoaluminum compounds, organozinc compounds, organomagnesiumcompounds, organolithium compounds, or any combination thereof. Morethan one co-catalyst can be present in the catalyst composition.

In particular aspects directed to catalyst compositions containing aco-catalyst and polymerization processes using a co-catalyst, theco-catalyst can comprise an aluminoxane compound (e.g., a supportedaluminoxane), an organoboron or organoborate compound, an ionizing ioniccompound, an organoaluminum compound, an organozinc compound, anorganomagnesium compound, or an organolithium compound, and thisincludes any combinations of these materials. In one aspect, theco-catalyst can comprise an organoaluminum compound. In another aspect,the co-catalyst can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, an organozinccompound, an organomagnesium compound, an organolithium compound, or anycombination thereof. In yet another aspect, the co-catalyst can comprisean aluminoxane compound; alternatively, an organoboron or organoboratecompound; alternatively, an ionizing ionic compound; alternatively, anorganozinc compound; alternatively, an organomagnesium compound; oralternatively, an organolithium compound.

Specific non-limiting examples of suitable organoaluminum compounds caninclude trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octyl aluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof. Representative andnon-limiting examples of aluminoxanes include methylaluminoxane,modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane,neopentylaluminoxane, and the like, or any combination thereof.Representative and non-limiting examples of organoboron/organoboratecompounds include N,N-dimethylaniliniumtetrakis-(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,and the like, or mixtures thereof.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)-borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl] borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl) borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and thelike, or combinations thereof.

Exemplary organozinc compounds which can be used as co-catalysts caninclude, but are not limited to, dimethylzinc, diethylzinc,dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc,di(triethylsilyl)zinc, di(triisoproplysilyl)zinc,di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc,di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.

Similarly, exemplary organomagnesium compounds can include, but are notlimited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium,dibutylmagnesium, dineopentylmagnesium,di(trimethylsilylmethyl)magnesium, methylmagnesium chloride,ethylmagnesium chloride, propylmagnesium chloride, butylmagnesiumchloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesiumchloride, methylmagnesium bromide, ethylmagnesium bromide,propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesiumbromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide,ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide,neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide,methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesiumethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide,trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide,ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesiumpropoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesiumpropoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide,propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesiumphenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or anycombinations thereof.

Likewise, exemplary organolithium compounds can include, but are notlimited to, methyllithium, ethyllithium, propyllithium, butyllithium(e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium,phenyllithium, tolyllithium, xylyllithium, benzyllithium,(dimethylphenyl)methyllithium, allyllithium, and the like, orcombinations thereof.

Co-catalysts that can be used in the catalyst compositions andpolymerization processes of this invention are not limited to theco-catalysts described above. Other suitable co-catalysts are well knownto those of skill in the art including, for example, those disclosed inU.S. Pat. Nos. 3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938,5,919,983, 7,294,599 7,601,665, 7,884,163, 8,114,946, and 8,309,485.

Any suitable metallocene compound can be used in the catalystcomposition. For example, the metallocene component of the catalystsystems provided herein can, in some aspects, comprise an unbridgedmetallocene; alternatively, an unbridged zirconium or hafnium basedmetallocene compound; alternatively, an unbridged zirconium or hafniumbased metallocene compound containing two cyclopentadienyl groups, twoindenyl groups, or a cyclopentadienyl and an indenyl group;alternatively, an unbridged zirconium based metallocene compoundcontaining two cyclopentadienyl groups, two indenyl groups, or acyclopentadienyl and an indenyl group. These cyclopentadienyl groups andindenyl groups, independently, can be unsubstituted or can besubstituted with any suitable substituent (one or more than one).Illustrative and non-limiting examples of unbridged metallocenecompounds (e.g., with zirconium or hafnium) that can be employed incatalyst systems consistent with aspects of the present invention aredescribed in U.S. Pat. Nos. 7,199,073, 7,226,886, 7,312,283, and7,619,047.

In other aspects, the metallocene component of the catalyst compositionsprovided herein can comprise a bridged metallocene compound, e.g., withtitanium, zirconium, or hafnium, such as a bridged zirconium or hafniumbased metallocene compound with a fluorenyl group; or alternatively, abridged zirconium or hafnium based metallocene compound with acyclopentadienyl group and a fluorenyl group. These cyclopentadienylgroups and fluorenyl groups, independently, can be unsubstituted or canbe substituted with any suitable substituent (one or more than one). Forinstance, such bridged metallocenes can contain an alkenyl substituent(e.g., a terminal alkenyl) on the bridging group, on acyclopentadienyl-type group (e.g., a cyclopentadienyl group or afluorenyl group), or on the bridging group and the cyclopentadienyl-typegroup. In some aspects, the metallocene catalyst component can comprisea bridged zirconium or hafnium based metallocene compound with afluorenyl group, and an aryl group on the bridging group; alternatively,a bridged zirconium or hafnium based metallocene compound with acyclopentadienyl group and fluorenyl group, and an aryl group on thebridging group; alternatively, a bridged zirconium based metallocenecompound with a fluorenyl group, and an aryl group on the bridginggroup; or alternatively, a bridged hafnium based metallocene compoundwith a fluorenyl group, and an aryl group on the bridging group. Inthese and other aspects, the aryl group on the bridging group can be aphenyl group. Optionally, these bridged metallocenes can contain analkenyl substituent (e.g., a terminal alkenyl) on the bridging group, ona cyclopentadienyl-type group, or on both the bridging group and thecyclopentadienyl group. Illustrative and non-limiting examples ofbridged metallocene compounds (e.g., with zirconium or hafnium) that canbe employed in catalyst systems consistent with aspects of the presentinvention are described in U.S. Pat. Nos. 7,026,494, 7,041,617,7,226,886, 7,312,283, 7,517,939, and 7,619,047.

The catalyst composition can be produced in any manner, such as bycontacting the metallocene compound, the fluorided silica-coatedalumina, and the co-catalyst (if used) in any order or sequence.

Generally, the weight ratio of co-catalyst (e.g., an organoaluminumcompound) to fluorided silica-coated alumina can be in a range from 10:1to 1:1000. If more than one co-catalyst compound and/or more than onefluorided silica-coated alumina are employed, this ratio is based on thetotal weight of each respective component. In another aspect, the weightratio of the co-catalyst to the fluorided silica-coated alumina can bein a range from 3:1 to 1:500, or from 1:10 to 1:350.

In some aspects of this invention, the weight ratio of metallocenecomplex to the fluorided silica-coated alumina can be in a range from1:1 to 1:1,000,000. If more than one metallocene compound and/or morethan one fluorided silica-coated alumina is/are employed, this ratio isbased on the total weights of the respective components. In anotheraspect, this weight ratio can be in a range from 1:5 to 1:100,000, orfrom 1:10 to 1:10,000. Yet, in another aspect, the weight ratio of themetallocene to the fluorided silica-coated alumina can be in a rangefrom 1:20 to 1:1000.

Catalyst compositions of the present invention generally have a catalystactivity greater than 2,000 grams, greater than 3,000 grams, greaterthan 4,000 grams, greater than grams, etc., of ethylene polymer(homopolymer or copolymer, as the context requires) per gram of thefluorided silica-coated alumina per hour (abbreviated g/g/hr). Inanother aspect, the catalyst activity can range from 3,000 to 20,000,from 4,000 to 15,000, or from 4,000 to 9,000 grams of polyethylene pergram of the fluorided silica-coated alumina per hour (g/g/hr). Theseactivities are measured under slurry polymerization conditions, with atriisobutylaluminum co-catalyst, using isobutane as the diluent, at apolymerization temperature of 75 to 100° C. (e.g., 95° C.) and a reactorpressure of 300 (2.07 MPa) to 500 psig (3.45 MPa) (e.g., 400 psig (2.76MPa)). Additionally, an excess of the metallocene compound in thecatalyst composition can be used (e.g.,1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methane zirconium dichloride).

Additionally or alternatively, catalyst compositions of the presentinvention generally have a catalyst activity greater than 100,000 grams,greater than 150,000 grams, greater than 200,000 grams, etc., ofethylene polymer (homopolymer or copolymer, as the context requires) pergram of the metallocene compound per hour (abbreviated g/g/hr). Inanother aspect, the catalyst activity may range from 100,000 to1,000,000, from 150,000 to 600,000, or from 200,000 to 500,000 g/g/hr.These activities are measured under slurry polymerization conditions,with a triisobutylaluminum co-catalyst, using isobutane as the diluent,at a polymerization temperature of 75 to 100° C. (e.g., 95° C.) and areactor pressure of 300 (2.07 MPa) to 500 psig (3.45 MPa) (e.g., 400psig (2.76 MPa)).

Polymerization Processes

Olefin polymers (e.g., ethylene polymers) can be produced from thedisclosed catalyst compositions using any suitable polymerizationprocess using various types of polymerization reactors, polymerizationreactor systems, and polymerization reaction conditions. Apolymerization process can comprise contacting any catalyst compositiondisclosed herein with an olefin monomer and an optional olefin comonomerin a polymerization reactor system under polymerization conditions toproduce an olefin polymer. This invention also encompasses any olefinpolymers (e.g., ethylene polymers) produced by the polymerizationprocesses disclosed herein.

As used herein, a “polymerization reactor” includes any polymerizationreactor capable of polymerizing olefin monomers and comonomers (one ormore than one comonomer) to produce homopolymers, copolymers,terpolymers, and the like. The various types of polymerization reactorsinclude those that can be referred to as a batch reactor, slurryreactor, gas-phase reactor, solution reactor, high pressure reactor,tubular reactor, autoclave reactor, and the like, or combinationsthereof; or alternatively, the polymerization reactor system cancomprise a slurry reactor, a gas-phase reactor, a solution reactor, or acombination thereof. The polymerization conditions for the variousreactor types are well known to those of skill in the art. Gas phasereactors can comprise fluidized bed reactors or staged horizontalreactors. Slurry reactors can comprise vertical or horizontal loops.High pressure reactors can comprise autoclave or tubular reactors.Reactor types can include batch or continuous processes. Continuousprocesses can use intermittent or continuous product discharge.Polymerization reactor systems and processes also can include partial orfull direct recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

A polymerization reactor system can comprise a single reactor ormultiple reactors (2 reactors, more than 2 reactors) of the same ordifferent type. For instance, the polymerization reactor system cancomprise a slurry reactor, a gas-phase reactor, a solution reactor, or acombination of two or more of these reactors. Production of polymers inmultiple reactors can include several stages in at least two separatepolymerization reactors interconnected by a transfer device making itpossible to transfer the polymer resulting from the first polymerizationreactor into the second reactor. The desired polymerization conditionsin one of the reactors can be different from the operating conditions ofthe other reactor(s). Alternatively, polymerization in multiple reactorscan include the manual transfer of polymer from one reactor tosubsequent reactors for continued polymerization. Multiple reactorsystems can include any combination including, but not limited to,multiple loop reactors, multiple gas phase reactors, a combination ofloop and gas phase reactors, multiple high pressure reactors, or acombination of high pressure with loop and/or gas phase reactors. Themultiple reactors can be operated in series, in parallel, or both.Accordingly, the present invention encompasses polymerization reactorsystems comprising a single reactor, comprising two reactors, andcomprising more than two reactors. The polymerization reactor system cancomprise a slurry reactor, a gas-phase reactor, a solution reactor, incertain aspects of this invention, as well as multi-reactor combinationsthereof.

According to one aspect, the polymerization reactor system can compriseat least one loop slurry reactor comprising vertical or horizontalloops. Monomer, diluent, catalyst, and comonomer can be continuously fedto a loop reactor where polymerization occurs. Generally, continuousprocesses can comprise the continuous introduction of monomer/comonomer,a catalyst, and a diluent into a polymerization reactor and thecontinuous removal from this reactor of a suspension comprising polymerparticles and the diluent. Reactor effluent can be flashed to remove thesolid polymer from the liquids that comprise the diluent, monomer and/orcomonomer. Various technologies can be used for this separation stepincluding, but not limited to, flashing that can include any combinationof heat addition and pressure reduction, separation by cyclonic actionin either a cyclone or hydrocyclone, or separation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415, and8,822,608. Suitable diluents used in slurry polymerization include, butare not limited to, the monomer being polymerized and hydrocarbons thatare liquids under reaction conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used.

According to yet another aspect, the polymerization reactor system cancomprise at least one gas phase reactor (e.g., a fluidized bed reactor).Such reactor systems can employ a continuous recycle stream containingone or more monomers continuously cycled through a fluidized bed in thepresence of the catalyst under polymerization conditions. A recyclestream can be withdrawn from the fluidized bed and recycled back intothe reactor. Simultaneously, polymer product can be withdrawn from thereactor and new or fresh monomer can be added to replace the polymerizedmonomer. Such gas phase reactors can comprise a process for multi-stepgas-phase polymerization of olefins, in which olefins are polymerized inthe gaseous phase in at least two independent gas-phase polymerizationzones while feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. Representative gasphase reactors are disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790,5,436,304, 7,531,606, and 7,598,327.

According to still another aspect, the polymerization reactor system cancomprise a high pressure polymerization reactor, e.g., can comprise atubular reactor or an autoclave reactor. Tubular reactors can haveseveral zones where fresh monomer, initiators, or catalysts are added.Monomer can be entrained in an inert gaseous stream and introduced atone zone of the reactor. Initiators, catalysts, and/or catalystcomponents can be entrained in a gaseous stream and introduced atanother zone of the reactor. The gas streams can be intermixed forpolymerization. Heat and pressure can be employed appropriately toobtain optimal polymerization reaction conditions.

According to yet another aspect, the polymerization reactor system cancomprise a solution polymerization reactor wherein the monomer/comonomerare contacted with the catalyst composition by suitable stirring orother means. A carrier comprising an inert organic diluent or excessmonomer can be employed. If desired, the monomer/comonomer can bebrought in the vapor phase into contact with the catalytic reactionproduct, in the presence or absence of liquid material. Thepolymerization zone can be maintained at temperatures and pressures thatwill result in the formation of a solution of the polymer in a reactionmedium. Agitation can be employed to obtain better temperature controland to maintain uniform polymerization mixtures throughout thepolymerization zone. Adequate means are utilized for dissipating theexothermic heat of polymerization.

The polymerization reactor system can further comprise any combinationof at least one raw material feed system, at least one feed system forcatalyst or catalyst components, and/or at least one polymer recoverysystem. Suitable reactor systems can further comprise systems forfeedstock purification, catalyst storage and preparation, extrusion,reactor cooling, polymer recovery, fractionation, recycle, storage,loadout, laboratory analysis, and process control. Depending upon thedesired properties of the olefin polymer, hydrogen can be added to thepolymerization reactor as needed (e.g., continuously or pulsed).

Polymerization conditions that can be controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. Various polymerization conditions can beheld substantially constant (such as within +/−20%, +/−10%, or +/−5%),for example, for the production of a particular grade of the olefinpolymer (or ethylene polymer). A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from 60° C. to280° C., for example, or from 60° C. to 120° C., depending upon the typeof polymerization reactor(s). In some reactor systems, thepolymerization temperature generally can be within a range from 70° C.to 105° C., or from 75° C. to 100° C.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at 200 to 500 psig (1.4 MPa to 3.4MPa). High pressure polymerization in tubular or autoclave reactors isgenerally run at 20,000 to 75,000 psig (138 to 517 MPa). Polymerizationreactors can also be operated in a supercritical region occurring atgenerally higher temperatures and pressures. Operation above thecritical point of a pressure/temperature diagram (supercritical phase)can offer advantages to the polymerization reaction process.

Olefin monomers that can be employed with the catalyst compositions andin the polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond, such as ethylene or propylene.In an aspect, the olefin monomer can comprise a C₂-C₂₀ olefin;alternatively, a C₂-C₂₀ alpha-olefin; alternatively, a C₂-C₁₀ olefin;alternatively, a C₂-C₁₀ alpha-olefin; alternatively, the olefin monomercan comprise ethylene; or alternatively, the olefin monomer can comprisepropylene (e.g., to produce a polypropylene homopolymer or apropylene-based copolymer).

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some aspects, the olefin monomer cancomprise ethylene or propylene, which is copolymerized with at least onecomonomer (e.g., a C₂-C₂₀ alpha-olefin or a C₃-C₂₀ alpha-olefin).According to one aspect of this invention, the olefin monomer used inthe polymerization process can comprise ethylene. In this aspect, thecomonomer can comprise a C₃-C₁₀ alpha-olefin; alternatively, thecomonomer can comprise 1-butene, 1-pentene, 1-hexene, 1-octene,1-decene, styrene, or any combination thereof; alternatively, thecomonomer can comprise 1-butene, 1-hexene, 1-octene, or any combinationthereof; alternatively, the comonomer can comprise 1-butene;alternatively, the comonomer can comprise 1-hexene; or alternatively,the comonomer can comprise 1-octene.

Polymers and Articles

Olefin polymers encompassed herein can include any polymer produced fromany olefin monomer and optional comonomer(s) described herein. Forexample, the olefin polymer can comprise an ethylene homopolymer, anethylene copolymer (e.g., ethylene/α-olefin, ethylene/1-butene,ethylene/1-hexene, ethylene/1 -octene, etc.), a propylene homopolymer, apropylene copolymer, an ethylene terpolymer, a propylene terpolymer, andthe like, including any combinations thereof. In one aspect, the olefinpolymer can be (or can comprise) an ethylene/1-butene copolymer, anethylene/1-hexene copolymer, or an ethylene/1 -octene copolymer, whilein another aspect, the olefin polymer can be (or can comprise) anethylene/1-hexene copolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the olefin polymers (e.g., ethylene polymers) of thisinvention, whose typical properties are provided below.

The densities of ethylene-based polymers disclosed herein often aregreater than or equal to 0.90 g/cm³, and less than or equal to 0.97g/cm³. Yet, in particular aspects, the density can be in a range from0.91 to 0.965 g/cm³, from 0.91 to 0.93 g/cm³, from 0.92 to 0.96 g/cm³,from 0.93 to 0.955 g/cm³, or from 0.94 to 0.955 g/cm³. While not beinglimited thereto, the ethylene polymer can have a high load melt index(HLMI) in a range from 0 to 100 g/10 min; alternatively, from 1 to 80g/10 min; alternatively, from 2 to 40 g/10 min; alternatively, from 2 to30 g/10 min; alternatively, from 1 to 20 g/10 min; or alternatively,from 50 to 100 g/10 min. In an aspect, ethylene polymers describedherein can have a ratio of Mw/Mn, or the polydispersity index, in arange from 2 to 40, from 5 to 40, from 7 to 25, from 8 to 15, from 2 to10, from 2 to 6, or from 2 to 4. Additionally or alternatively, theethylene polymer can have a weight-average molecular weight (Mw) in arange from 75,000 to 700,000, from 75,000 to 200,000, from 100,000 to500,000, from 150,000 to 350,000, or from 200,000 to 320,000 g/mol.Moreover, the olefin polymers can be produced with a single or dualmetallocene catalyst system containing zirconium and/or hafnium. In suchinstances, the olefin polymer or ethylene polymer can contain nomeasurable amount of Mg, V, Ti, and Cr, i.e., less than 0.1 ppm byweight. In further aspects, the olefin polymer or ethylene polymer cancontain, independently, less than 0.08 ppm, less than 0.05 ppm, or lessthan 0.03 ppm, of Mg, V, Ti, and Cr.

An illustrative and non-limiting example of a particular ethylenepolymer (e.g., an ethylene/α-olefin copolymer) encompassedherein—produced using the supported fluorided silica-coated aluminaswith the porosity and other attributes disclosed herein—can have a meltindex (MI) in a range from 0.1 to 10 g/10 min and a density in a rangefrom 0.91 to 0.96 g/cm³, and the ethylene polymer can contain from 70 to270 ppm solid oxide and from 2 to 18 ppm fluorine. The fluorine contentis based on the elemental weight of F, and generally, the fluorine isfrom an inorganic source used in the preparation of the fluoridedsilica-coated alumina. Due to the unexpectedly high catalytic activityand catalyst productivity of the disclosed fluorided silica-coatedaluminas, the resulting ethylene polymer has beneficially low amounts ofcatalyst residue.

The melt index of the ethylene polymer ranges from 0.1 to 10 g/10 min,but more often, the melt index falls within a range from 0.3 to 8, from0.5 to 5, from 0.8 to 3, or from to 2 g/10 min, and the like. Thedensity of the ethylene-based polymer often can range from 0.91 to 0.96or from 0.915 to 0.958 g/cm³. In one aspect, the density can range from0.916 to 0.956, from 0.917 to 0.954 in another aspect, and from 0.915 to0.952 g/cm³ in yet another aspect.

In an aspect, the ethylene polymer can have a Mw in a range from 25,000to 400,000, from 40,000 to 300,000, from 50,000 to 250,000, or from80,000 to 200,000 g/mol. Additionally or alternatively, the ethylenepolymers can have a ratio of Mw/Mn in a range from 2 to 25, from 2.1 to20, from 2.3 to 20, from 2 to 5, or from 8 to 25, and the like. Theethylene polymer can have a unimodal molecular weight distribution, suchas may be produced using a single metallocene catalyst, and thus wouldgenerally have a narrow MWD. Alternatively, the ethylene polymer canhave a bimodal molecular weight distribution, such as may be producedusing two metallocene catalysts, and thus would generally have a broadMWD.

As discussed herein, the ethylene polymer can be produced with ametallocene catalyst, therefore, chromium and Ziegler-Natta catalystsystems are not required. Therefore, the ethylene polymer can contain nomeasurable amount of magnesium, vanadium, titanium, or chromium(catalyst residue), i.e., less than 0.1 ppm by weight. In some aspects,the ethylene polymer can contain, independently, less than 0.08 ppm,less than ppm, or less than 0.03 ppm, of magnesium (or vanadium, ortitanium, or chromium). The amounts of these elements can be determinedby ICP analysis on a PerkinElmer Optima 8300 instrument. Polymer orarticle samples can be ashed in a Thermolyne furnace with sulfuric acidovernight, followed by acid digestion in a HotBlock with HCl and HNO₃(3:1 v:v).

Instead, the ethylene polymer typically contains from 70 to 270 ppmsolid oxide (such as silica-coated alumina) and from 2 to 18 ppmfluorine (by weight). Other illustrative ranges for the fluorine contentof the ethylene polymer include, but are not limited to, from 2 to 16ppm, from 2 to 14 ppm, from 2 to 12 ppm, from 2 to 10 ppm, from 3 to 16ppm, from 3 to 12 ppm, from 4 to 12 ppm, or from 4 to 10 ppm offluorine. Other illustrative ranges for the solid oxide content of theethylene polymer include, but are not limited to, from 70 to 250 ppm,from 100 to 250 ppm, from 100 to 200 ppm, from 100 to 150 ppm, from 120to 250 ppm, from 120 to 200 ppm, or from 120 to 170 ppm of solid oxide.The solid oxide content of the polymer is quantified by an ash test,discussed hereinbelow. While not required, the solid oxide can containsilica and alumina in any suitable relative amount, and illustrativeweight ratios of silica:alumina can include from 20:80 to 80:20, from20:80 to from 25:75 to 55:45, or from 35:65 to 45:55, and so forth. Theethylene polymer also contains residual metal from the metallocenecompound, such as zirconium and/or hafnium (or titanium, if used).Generally, the ethylene polymer can contain from 0.5 to 5 ppm, from 0.5to 4 ppm, from 0.5 to 3 ppm, from 0.6 to 5 ppm, from 0.6 to 4 ppm, from0.6 to 3 ppm, from 0.7 to 4 ppm, or from 0.7 to 2.5 ppm of zirconium (orhafnium, or titanium).

Polymers of ethylene, whether homopolymers, copolymers, and so forth,can be formed into various articles of manufacture. Articles which cancomprise polymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, a toy,and the like. Various processes can be employed to form these articles.Non-limiting examples of these processes include injection molding, blowmolding, rotational molding, film extrusion, sheet extrusion, profileextrusion, thermoforming, and the like. Additionally, additives andmodifiers are often added to these polymers in order to providebeneficial polymer processing or end-use product attributes. Suchprocesses and materials are described in Modern Plastics Encyclopedia,Mid-November 1995 Issue, Vol. 72, No. 12; and Film ExtrusionManual—Process, Materials, Properties, TAPPI Press, 1992. In someaspects of this invention, an article of manufacture can comprise any ofolefin polymers (or ethylene polymers) described herein, and the articleof manufacture can be or can comprise a film (e.g., a blown film), apipe, or a molded product (e.g., a blow molded product).

Preparing Fluorided Silica-Coated Aluminas

A process for producing a fluorided silica-coated aluminaactivator-support is described herein. This process can comprise (orconsist essentially of, or consist of) contacting a fluoriding agentwith a silica-coated alumina to produce the fluorided silica-coatedalumina. The silica-coated alumina, prior to being combined with thefluoriding agent, has (or is characterized by) the following properties:a bulk density from 0.15 to 0.37 g/mL, a total pore volume from 1.1 to2.5 mL/g, a BET surface area from 250 to 600 m 2 /g, and an average porediameter from 10 to 25 nm. Generally, the features of this process(e.g., the fluoriding agent, the silica-coated alumina and itscharacteristics, and the fluorided silica-coated alumina and itscharacteristics, among others) are independently described herein, andthese features can be combined in any combination to further describethe disclosed process. Moreover, other process steps can be conductedbefore, during, and/or after any of the steps listed in the disclosedprocess, unless stated otherwise. Additionally, fluorided silica-coatedalumina activator-supports produced in accordance with the disclosedprocess are within the scope of this disclosure and are encompassedherein.

Typically, the silica-coated alumina starting material has a bulkdensity from 0.15 to 0.37 g/mL. Other representative and non-limitingranges for the bulk density include from to 0.32 g/mL, from 0.17 to 0.3g/mL, from 0.18 to 0.28 g/mL, or from 0.18 to 0.25 g/mL, and the like.The total pore volume of the silica-coated alumina can range from 1.1 to2.5 mL/g, while the BET surface area can range from 250 to 600 m²/g. Insome aspects, the total pore volume can range from 1.2 to 2.2 mL/g;alternatively, from 1.3 to 2.4 mL/g; alternatively, from 1.4 to 2 mL/g;or alternatively, from 1.3 to 1.8 mL/g. Likewise, the BET surface area,in some aspects, can range from 300 to 550 m²/g; alternatively, from 300to 500 m²/g; or alternatively, from 325 to 475 m²/g.

The silica-coated alumina has a significant amount of larger pores, andone particular measurable parameter is the average pore diameter innanometers (4000*PVISA, with PV in mL/g and SA in m²/g). For example, asilica-coated alumina with a total pore volume of 1.6 mL/g and a totalBET surface area of 410 m²/g translates to an average pore diameter ofnm. While not limited thereto, the silica-coated alumina startingmaterial can have an average pore diameter from 10 to 20 nm in oneaspect, from 11 to 19 nm in another aspect, from 12 to 20 nm in yetanother aspect, and from 12 to 18 nm in still another aspect.

The silica-coated alumina can contain any suitable amount of silica,based on the weight of the silica-coated alumina. Representative rangesinclude from 10 to 80 wt. % silica, from 20 to 60 wt. % silica, from 25to 55 wt. % silica, or from 35 to 45 wt. % silica, and the like.

While not limited thereto, the process to produce the fluoridedsilica-coated alumina activator-support can be performed by contactingthe fluoriding agent and the silica-coated alumina in water to form anaqueous mixture containing the fluorided silica-coated alumina. Theorder in which the components are combined to produce the aqueousmixture is not particularly limited. In one aspect, for instance, thefluoriding agent can be contacted first with water, and then thesilica-coated alumina can be introduced, while in another aspect, thesilica-coated alumina can be contacted first with water, and then thefluoriding agent can be introduced. Yet, in another aspect, thesecomponents can be contacted substantially contemporaneously, which inthis context, means that the fluoriding agent, the silica-coatedalumina, and water are contacted together as soon as commerciallypracticable, such as within 15 min, within 5 min, or within 1 min, oftwo of the components being contacted (e.g., water and either thefluoriding agent or the silica-coated alumina).

Any suitable fluoriding agent or fluorine-containing compound can beused to produce the fluorided silica-coated alumina. Illustrative andnon-limiting examples of the fluoriding agent include hydrogen fluoride(HF), ammonium bifluoride (NH₄HF₂), triflic acid (CF₃SO₃H),tetrafluoroboric acid (HBF₄), hexafluorosilicic acid (H₂SiF₆),hexafluorophosphoric acid (HPF₆), zinc tetrafluoroborate (Zn(BF₄)₂), andthe like. Combinations of two or more fluoriding agents can be used, ifdesired. In an aspect, the fluoriding agent can comprise (or consistessentially of, or consist of) hydrogen fluoride (HF); alternatively,ammonium bifluoride (NH₄HF₂); alternatively, triflic acid (CF₃SO₃H);alternatively, tetrafluoroboric acid (HBF₄); alternatively,hexafluorosilicic acid (H₂SiF₆); alternatively, hexafluorophosphoricacid (HPF₆); or alternatively, zinc tetrafluoroborate (Zn(BF₄)₂).

The fluoriding agent and the silica-coated alumina can be contacted orcombined at any suitable pH, and at a variety of temperatures and timeperiods. Generally, ambient temperatures are conveniently used, and hightemperatures are typically avoided, in order to prevent gaseous fluorinecompounds from being released.

The process to produce the fluorided silica-coated aluminaactivator-support can further comprise a step of drying the fluoridedsilica-coated alumina, and any suitable technique can be utilized. Forinstance, excess liquid can be removed from the fluorided silica-coatedalumina (e.g., draining, filtering, decanting, pressing, centrifuging,etc.), and the wet fluorided silica-coated alumina can be subjected to awide range of drying times, drying temperatures, and drying pressures.For example, the drying time can range from 15 min to 48 hr, from 30 minto 24 hr, or from 1 to 12 hr, and the drying temperature can range from50° C. to 300° C., from 95° C. to 300° C., or from 100° C. to 275° C.The drying pressure can be at or around atmospheric pressure, but inmany instances, the drying step can be conducted under vacuum conditionsat any suitable sub-atmospheric pressure, such as less than 100 torr(13.3 kPa), less than 50 (6.67 kPa) torr, or less than 10 torr (1.33kPa).

Various types of dryer devices can be used for the drying step, such astray dryers, rotary dryers, fluidized bed dryers, and spray dryers,although not limited thereto. In a particular aspect of this invention,the drying step comprises spray drying the (wet) fluorided silica-coatedalumina (e.g., a slurry or suspension of the fluorided silica-coatedalumina in water) to a dried particulate or powder form. For spraydrying, the drying times are different from those described above withdrying times of less than 30 min, less than 20 min, less than min, lessthan 5 min, or even less than 1 min.

Optionally, after drying, the fluorided silica-coated alumina can becalcined, which can be conducted at a variety of temperatures and timeperiods. Typical peak calcining temperatures often fall within a rangefrom 400° C. to 1000° C., such as from 400° C. to 900° C., from 500° C.to 800° C., or from 550° C. to 700° C. In these and other aspects, thesetemperature ranges also are meant to encompass circumstances where thecalcination step is conducted at a series of different temperatures(e.g., an initial calcination temperature, a peak calcinationtemperature), instead of at a single fixed temperature, falling withinthe respective ranges, wherein at least one temperature is within therespective ranges.

The duration of the calcining step is not limited to any particularperiod of time. Hence, the calcining step can be conducted, for example,in a time period ranging from as little as 30-45 min to as long as 36-48hr, or more. The appropriate calcining time can depend upon, forexample, the initial/peak calcining temperature, among other variables.Generally, however, the calcining step can be conducted in a time periodthat can be in a range from 30 min to 48 hr, such as, for example, from1 hr to 24 hr, from 1 hr to 12 hr, from 2 hr to 12 hr, or from 2 hr to 8hr.

The calcining step can be conducted in a calcining gas stream thatcomprises (or consists essentially of, or consists of) an inert gas(e.g., nitrogen), oxygen, air, or any mixture or combination thereof. Insome aspects, the calcining gas stream can comprise air, while in otheraspects, the calcining gas stream can comprise a mixture of air andnitrogen. Yet, in certain aspects, the calcining gas stream can be aninert gas, such as nitrogen and/or argon.

The calcining step can be conducted using any suitable technique andequipment, whether batch or continuous. For instance, the calcining stepcan be performed in a belt calciner or, alternatively, a rotarycalciner. In some aspects, the calcining step can be performed in abatch or continuous calcination vessel comprising a fluidized bed. Aswould be recognized by those of skill in the art, other suitabletechniques and equipment can be employed for the calcining step, andsuch techniques and equipment are encompassed herein.

The fluorided silica-coated alumina produced by the disclosed processcan have any of the properties or features disclosed hereinabove, e.g.,a bulk density from 0.15 to 0.37 g/mL, a total pore volume from 0.85 to2 mL/g, a BET surface area from 200 to 500 m 2 /g, an average porediameter from 10 to 25 nm, from 80 to 99% of the pore volume in poreswith diameters of greater than 6 nm, and the like. Further, thefluorided silica-coated alumina can be produced with any targeted amountof fluorine, such as from 0.5 to 18 wt. % F, from 1 to 13 wt. % F, from2 to 9 wt. % F, from 3 to 16 wt. % F, or from 3 to 10 wt. % F, based onthe weight of the fluorided silica-coated alumina.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, modifications, and equivalentsthereof, which after reading the description herein, can suggestthemselves to one of ordinary skill in the art without departing fromthe spirit of the present invention or the scope of the appended claims.

For silica-coated alumina and fluorided silica-coated aluminacharacterization, about 0.2 grams of sample were degassed in aphysisorption tube, using a Quantachrome Instruments NOVATOUCH® SurfaceArea and Pore Volume Analyzer. To prevent portions of the fine particlesfrom boiling up to a region of the sample tube not in the heated zone,the pressure was reduced gradually, and the temperature was increasedstepwise. The pressure was initially reduced from ambient to 1 mm Hg, ata controlled rate of 5 mm Hg/s, while holding the samples at 30° C.After reaching sufficient vacuum (˜0.1 mm Hg), the temperature wasincreased to 80° C. and held for 30 min, then to 150° C. and held for 30min, then to 250° C. and held for 720 min, with the final vacuumreaching a pressure of about 1 Millitorr. After cooling to ambient, thesamples were backfilled with nitrogen and analyzed on the samephysisorption instrument. Approximately 39 adsorption points werecollected to construct an isotherm, and software packages included withthe instrument were used to determine surface areas, pore volumes, andto generate pore size distribution curves. Surface areas were determinedusing the BET method (Brunauer, J. Am Chem. Soc., 1938, 60, 309), fromadsorption isotherm points having P/Po values from 0.0 to 0.2. Porevolume values were calculated from the isotherm point having a P/Povalue closest to 0.982. Pore size distributions were generated fromdesorption isotherm data using the BJH method (J. Am. Chem. Soc., 1951,73, 373), with thickness curves generated using the Halsey equation (J.Chem. Phys., 1948, 16, 931). Total pore volumes were determined inaccordance with Halsey (J. Chem. Phys., 1948, 16, 931).

Bulk density measurements were determined in accordance with ASTMD6683-19. The d50 particle size, or median or average particle size,refers to the particle size for which 50% of the sample has a smallersize and 50% of the sample has a larger size. Particle sizedistributions (inclusive of d10, d50, and d90) were determined usinglaser diffraction in accordance with ISO 13320.

Melt rheological characterizations were performed as follows.Small-strain (less than 10%) oscillatory shear measurements wereperformed on an ANTON PAAR® MCR rheometer using parallel-plate geometry.All rheological tests were performed at 190° C. The complex viscosity|η*| versus frequency (w) data were then curve fitted using the modifiedthree parameter Carreau-Yasuda (CY) empirical model to obtain the zeroshear viscosity—η₀, characteristic viscous relaxation time—ρ_(η), andthe breadth parameter—a (CY-a parameter). The simplified Carreau-Yasuda(CY) empirical model is as follows.

${{❘{\eta^{*}(\omega)}❘} = \frac{\eta_{0}}{\left\lbrack {1 + \left( {\tau_{\eta}\omega} \right)^{a}} \right\rbrack^{{({1 - n})}/a}}},$

wherein: |η*(ω)|=magnitude of complex shear viscosity;

-   -   η₀=zero shear viscosity;    -   τ_(η)=viscous relaxation time (Tau(η));    -   a=“breadth” parameter (CY-a parameter);    -   n=fixes the final power law slope, fixed at 2/11; and    -   ω=angular frequency of oscillatory shearing deformation.

Details of the significance and interpretation of the CY model andderived parameters can be found in: C. A. Hieber and H. H. Chiang,Rheol. Acta, 28, 321 (1989); C.A. Hieber and H. H. Chiang, Polym. Eng.Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger,Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition,John Wiley & Sons (1987).

Melt index (MI, g/10 min) can be determined in accordance with ASTMD1238 at 190° C. with a 2,160 gram weight. Density can be determined ingrams per cubic centimeter (g/cm³) on a compression molded sample,cooled at 15° C. per minute, and conditioned for hours at roomtemperature in accordance with ASTM D1505 and ASTM D4703.

Molecular weights and molecular weight distributions can be obtainedusing a PL-GPC 220 (Polymer Labs, an Agilent Company) system equippedwith a IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPCcolumns (Waters, MA) running at 145° C. The flow rate of the mobilephase 1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) is set at 1 mL/min, and polymersolution concentrations are in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation is conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions are transferred to sample vials for injection. An injectionvolume of about 400 μL is used. The integral calibration method is usedto deduce molecular weights and molecular weight distributions using aChevron Phillips Chemical Company's HDPE polyethylene resin, MARLEX®BHB5003, as the broad standard. An integral table of the broad standardis pre-determined in a separate experiment with SEC-MALS. Mn is thenumber-average molecular weight, Mw is the weight-average molecularweight, Mz is the z-average molecular weight, Mv is theviscosity-average molecular weight, and Mp is the peak molecular weight(location, in molecular weight, of the highest point of the molecularweight distribution curve).

Herein, the ASTM ash content of the polymer (measured by ASTM D5630-13,procedure B) encompasses the amount of solid oxide (e.g., silica-coatedalumina), metallocene transition metal, and fluorine. Since themetallocene transition metal and fluorine are minor portions of the ashcontent, the ash content is very close to the solid oxide content, butsolid oxide content herein equals ash content minus metallocenetransition metal content and minus fluorine content.

Metal content, such as from the transition metal of the metallocenecompound, can be determined by ICP analysis on a PerkinElmer Optima 8300instrument. Polymer or article samples can be ashed in a Thermolynefurnace with sulfuric acid overnight, followed by acid digestion in aHotBlock with HCl and HNO₃ (3:1 v:v).

Fluoride content was determined by direct weight of the fluoridecompound added. Additionally, fluoride content can be determined byX-ray fluorescence, using calibrated samples of known fluoride content.In all cases, the fluoride added remained on the support aftercalcination, indicating no loss due to evaporation.

Comparative and Inventive Examples 1-2

Two silica-coated alumina supports were obtained from Sasol Olefins &Surfactants GmbH under the designations of Siral® 40 (ComparativeExample 1, CE-1) and Siral® 40 HPV (Inventive Example 1, IE-1), and eachcontained 40 wt. % silica and 60 wt. % alumina, 10 based on the dryweight composition. Both supports were then treated with an aqueoussolution of hydrofluoric acid to yield approximately 5 wt. % fluorinebased on the dry weight of the support. The particles were dried,yielding a white powder. A 10-g sample of each powder product was thencalcined in dry air in a fluidized bed at 600° C. for three hr, cooledto room temperature, and flushed with dry nitrogen for 30 min. Thefluorided silica-coated alumina powder product (Comparative Example 2(CE-2) and Inventive Example 2 (IE-2)) were stored under nitrogen forlater use.

FIGS. 1-2 illustrate the pore volume distributions and surface areadistributions, respectively, as a function of pore diameter (nm) for thesilica-coated aluminas of CE-1 and IE-1, while FIGS. 3-4 illustrate thepore volume distributions and surface area distributions as a functionof pore diameter (nm) for the fluorided silica-coated aluminas of CE-2and IE-2. Some of the data expressed graphically in FIGS. 1-4 istabulated in Table I. Table I shows the result of summing up the porevolume and the surface area into several pore size categories, using theraw data obtained from nitrogen desorption curves. Data is expressed inpercentages as well as in absolute terms: mL/g for pore volume and m²/gfor surface area. Particle size testing of the fluorided silica-coatedaluminas of CE-2 and IE-2, presented in FIGS. 3-4 and Table I, wasperformed after drying and calcining of the respective fluoridedsilica-coated aluminas.

Referring first to the CE-1 and IE-1 silica-coated aluminas in thefigures and data table, the total pore volume of IE-1 was significantlyincreased over CE-1, but in addition, there were also large increases inthe average pore diameter, the peak pore diameter, and the respectiveamounts of pore volume and surface area present in larger pores.

After fluoriding, drying, and calcining, the figures and data table alsodemonstrate the same beneficial improvements for the fluoridedsilica-coated alumina of IE-2 as compared to CE-2. Although the overallpore volume was not increased as dramatically as for the silica-coatedalumina base material, there were large increases in the average porediameter and the peak pore diameter (over 20%), and significantincreases in the respective amounts of pore volume and surface areapresent in larger pores for IE-2 as compared to CE-2. Advantageously,the IE-2 fluorided silica-coated alumina, as compared to CE-2, had amuch larger amount of meso-pores (generally, pores with a pore diametergreater than or equal to 10 nm), with a significant reduction in theamount of small pores (e.g., less than 6 nm in diameter).

FIG. 5 illustrates the particle size distributions of IE-2 and CE-2, andkey particle size distribution metrics for IE-2 are summarized in TableII. Very small particles, often referred to as fines, can be problematicin polymerization reactor systems. Beneficially, although the particlesize distribution of IE-2 was slightly broader than CE-2, only a verysmall fraction of IE-2 had a particle size of less than 10 μm (the d10particle size was 24.6 μm). The fluorided silica-coated alumina of IE-2had a d50 average particle size of 63 μm, a ratio of d90/d10 of 5.4, aratio of d90/d50 of 2.1, and a span of 1.7.

The ability of the fluorided silica-coated alumina (FSCA) of IE-2 toadsorb a metallocene compound also was compared to CE-2. The metallocenecompound (MET) was1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methane zirconium dichloride (a bridged cyclopentadienyl-fluorenylmetallocene compound with a carbon bridge substituted with a methyl anda terminal butenyl). First, a stock solution of the metallocene compound(MET) was prepared by dissolving 80 mg of MET in a solvent mixturecontaining 8 mL of toluene and 80 mL of heptane. The concentration ofMET in the stock solution was 0.91 mg/mL or 1.56 μmol/mL.

The adsorption experiments were performed by mixing 8 mL of the METstock solution with IE-2 and CE-2, respectively, at room temperature,then shaking the mixture for 1 min, then allowing the mixture to settlefor 15 min. The supernatant liquid from the mixture was measured byUV-Vis at 582 nm wavelength to determine the amount of MET in thesupernatant liquid. The amount of MET adsorbed on IE-2 or CE-2 wascalculated by subtracting the amount of MET left in the supernatantliquid from the amount of MET in the stock solution used in theexperiment.

Table III summarizes the adsorption experiments with IE-2 and CE-2. CE-2only adsorbed 51 micromoles of the MET metallocene compound per gram ofCE-2, whereas IE-2 unexpectedly adsorbed 98 micromoles of MET per gramof IE-2 (an increase of 92%). Stated another way, CE-2 only adsorbed0.087 molecules of the MET metallocene compound per nm² of surface areaof CE-2, whereas IE-2 unexpectedly adsorbed 0.178 molecules of MET pernm² of surface area of IE-2 (an increase of 104%). The molecules of METadsorbed per nm² of the surface area of the respective FSCA weredetermined using the BET surface area from Table I, the adsorption inμmol/g from Table III, and Avogadro's number.

While not wishing to be bound by the following theory, it is believedthat IE-2 has better contact (or dispersion) between silica and alumina,which generates more acid sites, which increases the absorptivity (andthe catalytic activity, discussed below). Thus, IE-2 effectively has agreater number of acid sites or a greater number of “ionizing” sitesthan does CE-2, and each site can adsorb one base molecule (the METmetallocene compound is a weak base) and subsequently ionize themetallocene base.

Polymerization Examples 3-12

The general procedure for the polymerization experiments was as follows.The polymerization experiments are summarized in Table IV, and wereconducted in a 1-gallon autoclave reactor, with isobutane diluent (˜2 L)used in all experiments. The fluorided silica-coated alumina (˜50 mg), 1mmol of TIBA (1 M solution in hexanes), and 0.5-1.0 mg of a metallocenecompound (which was1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methane zirconium dichloride; 1 mg/mL toluene solution) were charged tothe reactor, followed by isobutane addition. Excess metallocene wasutilized, so that the activity of the fluorided silica-coated aluminacould be evaluated. The contents of the reactor were stirred and heatedto the desired polymerization temperature of 90° C. Ethylene was thenintroduced into the reactor (no hydrogen or comonomer was added), andethylene was fed on demand to maintain the target pressure of 390 psig(2.69 MPa) for the desired reaction time of 30 min. The reactor wasmaintained at 90° C. throughout the run by an automated heating-coolingsystem. After venting of the reactor, purging, and cooling, theresulting polymer product was dried under reduced pressure.

Table IV summarizes the results of the polymerization experiments, whereExamples 3-8 used the CE-2 fluorided silica-coated alumina, Examples9-12 used the IE-2 fluorided silica-coated alumina, the catalystactivity is in units of grams of polymer per gram of fluoridedsilica-coated alumina per hour (g/g/hr), and the CY-a parameter of theresultant polymer was measured. Unexpectedly, the catalytic activityusing the fluorided silica-coated alumina of IE-2 was improved, onaverage, over 100% versus CE-2.

The Carreau-Yasuda “a” parameter (CY-a parameter) is particularlysensitive to small changes in the polymer, such as long chain branch(LCB) content. Surprisingly, given the significant differences incatalytic activity between Examples 3-8 and Examples 9-12, there was nodifference in the CY-a parameter, thus indicating that the basic polymerproperties were not appreciably changed.

Inventive Examples 13-16

Inventive Examples 14A-15A, similar to IE-1, each contained 40 wt. %silica and 60 wt. % alumina, while Inventive Example 13A contained 28wt. % silica and 72 wt. % alumina. Using the same fluoriding andcalcining procedures described above, IE-13A was treated with an aqueoussolution of HBF₄ to yield 12.5 wt. % F (IE-13B), and IE-14A was treatedwith an aqueous solution of HBF₄ to yield 5 wt. % F (IE-14B). IE-15A wasfirst calcined at 600° C. for three hr, and then treated with an aqueoussolution of HBF₄ to yield 7 wt. % F (IE-15B). The bulk densities forthese examples were in the 0.18 to 0.32 g/mL range.

Like Table I, Table V shows the result of summing up the pore volume andthe surface area into several pore size categories, using the raw dataobtained from nitrogen desorption curves. Data is expressed inpercentages as well as in absolute terms: mL/g for pore volume and m²/gfor surface area. After fluoriding, drying, and calcining, Table Vdemonstrates the same beneficial improvements as for the fluoridedsilica-coated alumina of IE-2 as compared to CE-2 in Table I. Ascompared to CE-2, the fluorided silica-coated alumina materials ofIE-13B, IE-14B, and IE-15B had higher pore volumes and much largeraverage pore diameters. Beneficially, the IE-13B, IE-14B, and IE-15Bfluorided silica-coated aluminas, as compared to CE-2, had a much largeramount of meso-pores (generally, pores with a pore diameter greater thanor equal to 10 nm), with a significant reduction in the amount of smallpores (e.g., less than 6 nm in diameter).

Like Table III, Table VI summarizes the adsorption experiments withIE-13B, IE-14B, IE-15B, and IE-16B (IE-16B was prepared similarly toIE-15B, except with 14 wt. % F). Unexpectedly, these inventive fluoridedsilica-coated alumina support materials adsorbed from 60 to over 120micromoles of MET per gram of the respective support. While CE-2 onlyadsorbed 0.087 molecules of the MET metallocene compound per nm² ofsurface area of CE-2, the inventive fluorided silica-coated aluminasupport materials in Table VI unexpectedly adsorbed from 0.13 to 0.21molecules of MET per nm² of surface area of the respective support.

TABLE I Fluorided Silica- Silica-Coated Increase Coated Alumina Alumina(IE versus CE) Example CE-2 IE-2 CE-1 IE-1 After F Before F BET surfacearea, m²/g 352 331 464 407  −6%  −12% Total PV, mL/g 0.840 0.963 0.9611.643   15%    71% Avg Pore diam, nm 9.54 11.65 8.28 16.15   22%    95%Peak Pore diam, nm 7.73 9.45 6.51 7.71   22%    18% Bulk density, g/mL0.32 0.21 — — −34% — PV > diam 6 nm, mL/g 0.664 0.863 0.702 1.611   30%  129% PV > diam 10 nm mL/g 0.313 0.390 0.471 1.000   24%   112% PV >diam 16 nm, mL/g 0.110 0.153 0.124 0.521   39%   319% PV > diam 20 nm,mL/g 0.078 0.112 0.089 0.234   43%   162% PV > diam 40 nm, mL/g 0.0270.045 0.034 0.164   65%   378% BJH desorption PV, mL/g 0.848 0.993 0.9241.703 — — PV > diam 6 nm, % 78.3% 86.9% 76.0% 94.6%   11%    25% PV >diam 10 nm, % 36.9% 39.3% 51.0% 58.7%    6%    15% PV > diam 16 nm, %13.0% 15.4% 13.4% 30.6%   19%   127% PV > diam 20 nm, %  9.2% 11.3% 9.7% 13.7%   22%    42% PV > diam 40 nm %  3.2%  4.5%  3.7%  9.6%   41%  159% SA > diam 6 nm, m²/g 239 307 251 479   28%    91% SA > diam 10nm, m²/g 72 88 75.4 198   21%   162% SA > diam 16 nm, m²/g 13 18 11.8 59  32%   397% SA > diam 20 nm, m²/g 7.4 11 8.6 11   44%    22% SA > diam40 nm, m²/g 1.3 2.1 1.6 7.6   57%   382% BJH desorption SA, m²/g 392 411435 545 — — SA > diam 6 nm, % 60.9% 74.6% 57.8% 88.0%   23%    52% SA >diam 10 nm, % 18.5% 21.4% 17.3% 36.3%   16%   109% SA > diam 16 nm, % 3.4%  4.3%  2.7% 10.7%   26%   297% SA > diam 20 nm, % 1.90% 2.61%1.98% 1.93%   38%   −2% SA > diam 40 nm % 0.33% 0.50% 0.36% 1.39%   50%  285%

TABLE II Example IE-2 Mv, mean, μm 73.3 Mn, number avg, μm 19.3 MA, areamean, μm 48.0 CS, surface area 0.125 Std Dev, μm 40.5 Mz, graphic mean68.9 σ1, graphic std. dev. 42.3 Ski, skewness 0.29 Kg, peakedness 1.12D10, μm 24.66 D20, μm 35.15 D30, μm 44.89 D40, μm 54.12 D50, μm 63.44D60, μm 73.71 D70, μm 85.97 D80, μm 102.8 D90, μm 132.2 D95, μm 164.1D90/D10 5.36 D90/D50 2.08 Span 1.69

TABLE III Fluorided Silica-Coated Alumina FSCA CE-2 IE-2 Weight FSCA mg105 103 MET stock solution mL 8 8 MET in stock solution mg/mL 0.91 0.91μmol/mL 1.56 1.56 mg 7.27 7.27 μmol 12.45 12.45 MET in the supernatantafter mg/mL 0.52 0.18 adsorption μmol/mL 0.89 0.30 mg 4.16 1.40 μmol7.13 2.40 MET adsorbed by FSCA mg 3.11 5.87 μmol 5.32 10.05 mg/g 29.657.0 μmol/g 50.7 97.6 molecules/nm² 0.087 0.178

TABLE IV Fluorided Silica- Support Activity CY-a Example Coated Alumina(g/g/hr) parameter 3 CE-2 3,042 — 4 CE-2 3,524 — 5 CE-2 3,532 0.4698 6CE-2 3,340 0.4150 7 CE-2 3,246 0.4570 8 CE-2 3,324 0.4676 9 IE-2 7,2440.4352 10 IE-2 7,192 0.4037 11 IE-2 7,376 0.4554 12 IE-2 7,728 0.4714

TABLE V Fluorided Silica-Coated Alumina Silica-Coated Alumina ExampleIE-13B IE-14B IE-15B IE-13A IE-14A IE-15A BET surface area, m²/g 270 424381 326 440 468 Total PV, mL/g 1.219 1.388 1.458 1.396 1.618 1.352 AvgPore diam, nm 18.07 13.11 15.30 17.15 14.69 11.55 PV > diam 6 nm, mL/g1.214 1.287 1.396 1.374 1.508 1.172 PV > diam 10 nm mL/g 0.874 0.7460.830 1.062 0.844 0.563 PV > diam 16 nm, mL/g 0.420 0.322 0.409 0.4680.463 0.281 PV > diam 20 nm, mL/g 0.324 0.242 0.312 0.336 0.368 0.216PV > diam 40 nm, mL/g 0.158 0.101 0.123 0.139 0.167 0.087 BJH desorptionPV, mL/g 1.256 1.426 1.519 1.420 1.673 1.376 PV > diam 6 nm, % 96.7%90.3% 91.9% 96.8% 90.1% 85.2% PV > diam 10 nm, % 69.6% 52.3% 54.7% 74.8%50.5% 40.9% PV > diam 16 nm, % 33.4% 22.6% 26.9% 33.0% 27.7% 20.4% PV >diam 20 nm, % 25.8% 17.0% 20.6% 23.7% 22.0% 15.7% PV > diam 40 nm %12.6%  7.1%  8.1%  9.8% 10.0%  6.3% SA > diam 6 nm, m²/g 324 407 427 358471 401 SA > diam 10 nm, m²/g 174 161 169 222 159 114 SA > diam 16 nm,m²/g 45 37 47 57 49 32 SA > diam 20 nm, m²/g 27 22 29 31 32 20 SA > diam40 nm, m²/g 7 5 6 7 8 4 BJH desorption SA, m²/g 356 519 519 391 596 562SA > diam 6 nm, % 91.0% 78.4% 82.3% 91.6% 79.1% 71.2% SA > diam 10 nm, %49.0% 31.1% 32.5% 56.9% 26.7% 20.2% SA > diam 16 nm, % 12.6%  7.1%  9.0%14.5%  8.2%  5.6% SA > diam 20 nm, %  7.6%  4.2%  5.7%  7.9%  5.4%  3.6%SA > diam 40 nm %  2.0%  0.9%  1.1%  1.7%  1.3%  0.7%

TABLE VI Example IE-13B IE-14B IE-15B IE-16B Silica, wt. % 28 40 40 40Total PV, mL/g 1.22 1.39 1.46 1.40 Pre-calcined No No Yes Yes Fluorine,wt. % 12.5 5 7 14 MET adsorbed, μmol/g 59.6 122.1 117.7 107.3 BETsurface area, m²/g 270 424 381 310 MET adsorbed, molecules/nm² 0.1330.173 0.186 0.208

The invention is described above with reference to numerous aspects andspecific examples. Many variations will suggest themselves to thoseskilled in the art in light of the above detailed description. All suchobvious variations are within the full intended scope of the appendedclaims. Other aspects of the invention can include, but are not limitedto, the following (aspects are described as “comprising” but,alternatively, can “consist essentially of” or “consist of”):

Aspect 1. A fluorided silica-coated alumina having (or characterized by)a bulk density from 0.15 to 0.37 g/mL, a total pore volume from 0.85 to2 mL/g, a BET surface area from 200 to 500 m²/g, and an average porediameter from 10 to 25 nm.

Aspect 2. A fluorided silica-coated alumina having (or characterized by)a bulk density from 0.15 to 0.37 g/mL, a total pore volume from 0.85 to2 mL/g, a BET surface area from 200 to 500 m²/g, and from 80 to 99% ofpore volume in pores with diameters of greater than 6 nm.

Aspect 3. The fluorided silica-coated alumina defined aspect 1 or 2,wherein the fluorided silica-coated alumina contains any suitable amountof silica or an amount of silica in any range disclosed herein, e.g.,from 10 to 80 wt. % silica, from 20 to 60 wt. % silica, from 25 to 55wt. % silica, or from 35 to 45 wt. % silica, based on the weight ofsilica-coated alumina.

Aspect 4. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina containsany suitable amount of fluorine or an amount of fluorine in any rangedisclosed herein, e.g., from 0.5 to 18 wt. % F, from 1 to 13 wt. % F,from 2 to 9 wt. % F, from 3 to 16 wt. % F, or from 3 to 10 wt. % F,based on the weight of the fluorided silica-coated alumina.

Aspect 5. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anysuitable average (d50) particle size or an average particle size in anyrange disclosed herein, e.g., from 30 to 150 microns, from 40 to 100microns, or from 45 to 85 microns.

Aspect 6. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the bulk density is in any suitable range orany range disclosed herein, e.g., from 0.15 to 0.32 g/mL, from 0.17 to0.3 g/mL, from 0.18 to 0.28 g/mL, or from 0.18 to 0.25 g/mL.

Aspect 7. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the total pore volume is in any suitablerange or any range disclosed herein, e.g., from 0.85 to 1.6 mL/g, from0.9 to 1.8 mL/g, from 0.9 to 1.5 mL/g, or from 1 to 1.7 mL/g.

Aspect 8. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the BET surface area is in any suitable rangeor any range disclosed herein, e.g., from 250 to 450 m²/g, from 200 to425 m²/g, or from 270 to 425 m²/g.

Aspect 9. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anaverage pore diameter in any suitable range or any range disclosedherein, e.g., from 10 to 20 nm, from 10.5 to 22 nm, from 11 to 22 nm, orfrom 11 to 19 nm.

Aspect 10. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anysuitable percentage of the pore volume in pores with diameters ofgreater than 6 nm or an amount in any range disclosed herein, e.g., from80 to 97%, from 82 to 99%, from 82 to 97%, from 83 to 98%, or from 84 to99%.

Aspect 11. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anysuitable percentage of the pore volume in pores with diameters ofgreater than 20 nm or an amount in any range disclosed herein, e.g.,from 9.5 to 30%, from 10 to 30%, from 10 to 27%, from 10.5 to 28%, orfrom 11 to 26%.

Aspect 12. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anysuitable percentage of the pore volume in pores with diameters ofgreater than 40 nm or an amount in any range disclosed herein, e.g.,from 3.5 to 15%, from 3.5 to 13%, from 4 to 15%, from 4 to 13%, or from5 to 15%.

Aspect 13. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anysuitable pore volume of pores with diameters of greater than 6 nm or anamount in any range disclosed herein, e.g., at least mL/g, at least 0.8mL/g, at least 0.85 mL/g, from 0.7 to 1.6 mL/g, from 0.7 to 1.4 mL/g,from 0.75 to 1.5 mL/g, from 0.8 to 1.6 mL/g, or from 0.8 to 1.4 mL/g.

Aspect 14. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anysuitable pore volume of pores with diameters of greater than 20 nm or anamount in any range disclosed herein, e.g., at least 0.09 mL/g, at least0.1 mL/g, from 0.09 to 0.4 mL/g, from 0.09 to 0.34 mL/g, from 0.1 to 0.4mL/g, from 0.1 to 0.36 mL/g, or from 0.11 to 0.34 mL/g.

Aspect 15. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anysuitable percentage of surface area in pores with diameters of greaterthan 6 nm or an amount in any range disclosed herein, e.g., from 65 to98%, from 65 to 94%, from 65 to 91%, from 68 to 94%, from 70 to 98%, orfrom 70 to 91%.

Aspect 16. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anysuitable percentage of surface area in pores with diameters of greaterthan 10 nm or an amount in any range disclosed herein, e.g., from 19.5to 55%, from 20 to 55%, from 20 to 50%, from 21 to 55%, or from 21 to50%.

Aspect 17. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anysuitable surface area of pores with diameters of greater than 6 nm or anamount in any range disclosed herein, e.g., at least 250 m²/g, at least275 m²/g, from 250 to 475 m²/g, or from 275 to 450 m²/g.

Aspect 18. The fluorided silica-coated alumina defined in any one of thepreceding aspects, wherein the fluorided silica-coated alumina has anysuitable surface area of pores with diameters of greater than 10 nm oran amount in any range disclosed herein, e.g., at least 78 m²/g, atleast 85 m²/g, from 78 to 200 m²/g, or from 85 to 180 m²/g.

Aspect 19. A catalyst composition comprising a metallocene compound, thefluorided silica-coated alumina defined in any one of the precedingaspects, and an optional co-catalyst.

Aspect 20. The composition defined in aspect 19, wherein the metallocenecompound comprises any suitable metallocene compound or any metallocenecompound disclosed herein.

Aspect 21. The composition defined in aspect 19 or 20, wherein themetallocene compound comprises an unbridged zirconium or hafnium basedmetallocene compound containing two cyclopentadienyl groups, two indenylgroups, or a cyclopentadienyl and an indenyl group.

Aspect 22. The composition defined in any one of aspects 19-21, whereinthe metallocene compound comprises a bridged zirconium or hafnium basedmetallocene compound with a fluorenyl group.

Aspect 23. The composition defined in any one of aspects 19-21, whereinthe metallocene compound comprises a bridged zirconium or hafnium basedmetallocene compound with a cyclopentadienyl group and a fluorenylgroup.

Aspect 24. The composition defined in any one of aspects 19-23, whereinthe catalyst composition comprises only one metallocene compound.

Aspect 25. The composition defined in any one of aspects 19-23, whereinthe catalyst composition comprises two or more metallocene compounds.

Aspect 26. The composition defined in any one of aspects 19-25, whereinthe catalyst composition comprises the co-catalyst, e.g., anyco-catalyst disclosed herein.

Aspect 27. The composition defined in aspect 26, wherein the co-catalystcomprises an aluminoxane compound, an organoboron or organoboratecompound, an ionizing ionic compound, an organoaluminum compound, anorganozinc compound, an organomagnesium compound, an organolithiumcompound, or any combination thereof.

Aspect 28. The composition defined in aspect 26, wherein the co-catalystcomprises any suitable organoaluminum compound or any organoaluminumcompound disclosed herein.

Aspect 29. The composition defined in any one of aspects 19-26, whereinthe catalyst composition is substantially free of aluminoxane compounds,organoboron or organoborate compounds, ionizing ionic compounds, orcombinations thereof.

Aspect 30. The composition defined in any one of aspects 19-29, whereina catalyst activity of the catalyst composition is in any rangedisclosed herein, e.g., from 3,000 to 20,000, from 4,000 to 15,000, orfrom 4,000 to 9,000 grams of ethylene polymer per gram of the fluoridedsilica-coated alumina per hr (additionally or alternatively, from100,000 to 1,000,000, from 150,000 to 600,000, or from 200,000 to500,000 grams of ethylene polymer per gram of the metallocene compoundper hour), under slurry polymerization conditions, with atriisobutylaluminum co-catalyst, using isobutane as the diluent, at apolymerization temperature of 75 to 100° C. (e.g., 95° C.) and a reactorpressure of 300 (2.07 MPa) to 500 psig (3.45 MPa) (e.g., 400 psig (2.76MPa)).

Aspect 31. An olefin polymerization process, the process comprisingcontacting the catalyst composition defined in any one of aspects 19-30with an olefin monomer and an optional olefin comonomer in apolymerization reactor system under polymerization conditions to producean olefin polymer.

Aspect 32. The olefin polymerization process defined in aspect 31,wherein the olefin monomer comprises any olefin monomer disclosedherein, e.g., any C₂-C₂₀ olefin.

Aspect 33. The olefin polymerization process defined in aspect 31,wherein the olefin monomer and the optional olefin comonomerindependently comprise a C₂-C₂₀ alpha-olefin.

Aspect 34. The olefin polymerization process defined in any one ofaspects 31-33, wherein the olefin monomer comprises ethylene.

Aspect 35. The olefin polymerization process defined in any one ofaspects 31-34, wherein the catalyst composition is contacted withethylene and an olefin comonomer comprising a C₃-C₁₀ alpha-olefin.

Aspect 36. The olefin polymerization process defined in any one ofaspects 31-35, wherein the catalyst composition is contacted withethylene and an olefin comonomer comprising 1-butene, 1-hexene,1-octene, or a mixture thereof.

Aspect 37. The olefin polymerization process defined in any one ofaspects 31-36, wherein the polymerization reactor system comprises abatch reactor, a slurry reactor, a gas-phase reactor, a solutionreactor, a high pressure reactor, a tubular reactor, an autoclavereactor, or a combination thereof.

Aspect 38. The olefin polymerization process defined in any one ofaspects 31-37, wherein the polymerization reactor system comprises aslurry reactor, a gas-phase reactor, a solution reactor, or acombination thereof.

Aspect 39. The olefin polymerization process defined in any one ofaspects 31-38, wherein the polymerization reactor system comprises aloop slurry reactor.

Aspect 40. The olefin polymerization process defined in any one ofaspects 31-39, wherein the polymerization reactor system comprises asingle reactor.

Aspect 41. The olefin polymerization process defined in any one ofaspects 31-39, wherein the polymerization reactor system comprises 2reactors.

Aspect 42. The olefin polymerization process defined in any one ofaspects 31-39, wherein the polymerization reactor system comprises morethan 2 reactors.

Aspect 43. The olefin polymerization process defined in any one ofaspects 31-42, wherein the olefin polymer comprises any olefin polymerdisclosed herein.

Aspect 44. The olefin polymerization process defined in any one ofaspects 31-43, wherein the olefin polymer comprises an ethylenehomopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, and/or an ethylene/1-octene copolymer.

Aspect 45. The olefin polymerization process defined in any one ofaspects 31-44, wherein the polymerization conditions comprise apolymerization reaction temperature in a range from 60° C. to 120° C.and a reaction pressure in a range from 200 to 1000 psig (from 1.4 to6.9 MPa).

Aspect 46. The olefin polymerization process defined in any one ofaspects 31-45, wherein the polymerization conditions are substantiallyconstant, e.g., for a particular polymer grade, such as within +/−20%,+/−10%, or +/−5%.

Aspect 47. The olefin polymerization process defined in any one ofaspects 31-46, wherein no hydrogen is added to the polymerizationreactor system.

Aspect 48. The olefin polymerization process defined in any one ofaspects 31-46, wherein hydrogen is added to the polymerization reactorsystem.

Aspect 49. An olefin polymer produced by the olefin polymerizationprocess defined in any one of aspects 31-48.

Aspect 50. A process to produce a fluorided silica-coated alumina, theprocess comprising contacting a fluoriding agent with a silica-coatedalumina to produce the fluorided silica-coated alumina, wherein thesilica-coated alumina has (or is characterized by) a bulk density from0.15 to 0.37 g/mL, a total pore volume from 1.1 to 2.5 mL/g, a BETsurface area from 250 to 600 m²/g, and an average pore diameter from 10to 25 nm.

Aspect 51. The process defined in aspect 50, wherein the fluoridingagent and the silica-coated alumina are contacted in water to form anaqueous mixture of the fluorided silica-coated alumina.

Aspect 52. The process defined in aspect 50 or 51, further comprising astep of drying the fluorided silica-coated alumina, a step of calciningthe fluorided silica-coated alumina, or both.

Aspect 53. The process defined in any one of aspects 50-52, wherein thefluoriding agent comprise hydrogen fluoride (HF), ammonium bifluoride(NH₄HF₂), triflic acid (CF₃SO₃H), tetrafluoroboric acid (HBF₄),hexafluorosilicic acid (H₂SiF₆), hexafluorophosphoric acid (HPF₆), zinctetrafluoroborate (Zn(BF₄)₂), or any combination thereof.

Aspect 54. The process defined in any one of aspects 50-52, wherein thefluoriding agent comprise hydrogen fluoride (HF).

Aspect 55. The process defined in any one of aspects 50-54, wherein thefluorided silica-coated alumina is defined by any one of aspects 1-18.

Aspect 56. A supported metallocene catalyst comprising a metallocenecompound and a fluorided silica-coated alumina, wherein an amount of themetallocene compound adsorbed per gram of the fluorided silica-coatedalumina is in any suitable range or in any range disclosed herein, e.g.,at least 55 μmol/g, at least 60 μmol/g, from 55 to 155 μmol/g, or from60 to at least 130 μmol/g.

Aspect 57. A supported metallocene catalyst comprising a metallocenecompound and a fluorided silica-coated alumina, wherein a number ofmolecules of the metallocene compound adsorbed per nm² of surface areaof the fluorided silica-coated alumina is in any suitable range or inany range disclosed herein, e.g., at least 0.1 molecules per nm², atleast molecules per nm², from 0.1 to 0.3 molecules per nm², from 0.1 to0.24 molecules per nm², or from 0.12 to 0.22 molecules per nm².

Aspect 58. The catalyst defined in aspect 56 or 57, wherein thesupported metallocene catalyst (or the fluorided silica-coated alumina)is defined by any one of aspects 1-18.

Aspect 59. An ethylene polymer having (or characterized by) a melt index(MI) in a range from 0.1 to 10 g/10 min and a density in a range from0.91 to 0.96 g/cm³, wherein the ethylene polymer contains from 70 to 270ppm solid oxide and from 2 to 18 ppm fluorine.

Aspect 60. The polymer defined in aspect 59, wherein the MI is in anyrange disclosed herein, e.g., from 0.3 to 8, from 0.5 to 5, from 0.8 to3, or from 0.5 to 2 g/10 min.

Aspect 61. The polymer defined in aspect 59 or 60, wherein the densityis in any range disclosed herein, e.g., from 0.915 to 0.958, from 0.916to 0.956, from 0.917 to 0.954, or from 0.915 to 0.952 g/cm³.

Aspect 62. The polymer defined in any one of aspects 59-61, wherein theethylene polymer contains from 70 to 250 ppm, from 100 to 250 ppm, from100 to 200 ppm, from 100 to 150 ppm, from 120 to 250 ppm, from 120 to200 ppm, or from 120 to 170 ppm of solid oxide.

Aspect 63. The polymer defined in any one of aspects 59-62, wherein theethylene polymer contains from 2 to 16 ppm, from 2 to 14 ppm, from 2 to12 ppm, from 2 to 10 ppm, from 3 to 16 ppm, from 3 to 12 ppm, from 4 to12 ppm, or from 4 to 10 ppm of fluorine.

Aspect 64. The polymer defined any one of aspects 59-63, wherein thesolid oxide contains silica and alumina in any suitable relative amountor a ratio of silica:alumina in any range disclosed herein, e.g., from20:80 to 80:20, from 20:80 to 60:40, from 25:75 to 55:45, or from 35:65to 45:55.

Aspect 65. The polymer defined in any one of aspects 59-64, wherein theethylene polymer contains from 0.5 to 5 ppm, from 0.5 to 4 ppm, from 0.5to 3 ppm, from 0.6 to 5 ppm, from 0.6 to 4 ppm, from 0.6 to 3 ppm, from0.7 to 4 ppm, or from 0.7 to 2.5 ppm of zirconium (or hafnium, ortitanium).

Aspect 66. The polymer defined in any one of aspects 59-65, wherein theethylene polymer contains, independently, less than 0.1 ppm (by weight),less than 0.08 ppm, less than 0.05 ppm, or less than 0.03 ppm, of Mg, V,Ti, or Cr.

Aspect 67. The polymer defined in any one of aspects 59-66, wherein theethylene polymer has a Mw in any range disclosed herein, e.g., from 25to 400, from 40 to 300, from to 250, or from 80 to 200 kg/mol.

Aspect 68. The polymer defined in any one of aspects 59-67, wherein theethylene polymer has a ratio of Mw/Mn in any range disclosed herein,e.g., from 2 to 25, from 2.1 to 20, from 2.3 to 20, from 2 to 5, or from8 to 25.

Aspect 69. The polymer defined in any one of aspects 59-68, wherein theethylene polymer has a unimodal molecular weight distribution.

Aspect 70. The polymer defined in any one of aspects 59-68, wherein theethylene polymer has a bimodal molecular weight distribution.

Aspect 71. The polymer defined in any one of aspects 59-70, wherein theethylene polymer comprises an ethylene homopolymer and/or anethylene/α-olefin copolymer.

Aspect 72. The polymer defined in any one of aspects 59-71, wherein theethylene polymer comprises an ethylene homopolymer, an ethylene/1-butenecopolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octenecopolymer.

Aspect 73. The polymer defined in any one of aspects 59-72, wherein theethylene polymer comprises an ethylene/1-hexene copolymer.

Aspect 74. The polymer defined in any one of aspects 59-73, wherein thepolymer is produced by the olefin polymerization process defined in anyone of aspects 31-48.

Aspect 75. An article (e.g., a film, pipe, or molded product) comprisingthe ethylene polymer defined in any one of aspects 59-74.

Aspect 76. An article comprising the ethylene polymer defined in any oneof aspects 59-74, wherein the article is an agricultural film, anautomobile part, a bottle, a container for chemicals, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, an outdoor storage product,outdoor play equipment, a pipe, a sheet or tape, a toy, or a trafficbarrier.

We claim:
 1. A fluorided silica-coated alumina having: a bulk densityfrom 0.15 to 0.37 g/mL; a total pore volume from 0.85 to 2 mL/g; a BETsurface area from 200 to 500 m²/g; and an average pore diameter from 10to 25 nm and/or from 80 to 99% of pore volume in pores with diameters ofgreater than 6 nm.
 2. The fluorided silica-coated alumina of claim 1,wherein the fluorided silica-coated alumina contains: from 10 to 80 wt.% silica, based on a weight of silica-coated alumina; and from 0.5 to 18wt. % F, based on a weight of the fluorided silica-coated alumina. 3.The fluorided silica-coated alumina of claim 1, wherein the fluoridedsilica-coated alumina has an average (d50) particle size from 30 to 150microns.
 4. The fluorided silica-coated alumina of claim 1, wherein: thebulk density is from 0.17 to 0.3 g/mL; the total pore volume is from 0.9to 1.5 mL/g; the BET surface area is from 250 to 450 m 2 /g; the averagepore diameter is from 10 to 20 nm; and from 83 to 98% of the pore volumeis in pores with diameters of greater than 6 nm.
 5. The fluoridedsilica-coated alumina of claim 1, wherein: from 9.5 to 30% of the porevolume is in pores with diameters of greater than 20 nm; from 3.5 to 15%of the pore volume is in pores with diameters of greater than 40 nm; thefluorided silica-coated alumina has a pore volume of from 0.7 to 1.6mL/g in pores with diameters of greater than 6 nm; and the fluoridedsilica-coated alumina has a pore volume of from 0.09 to 0.4 mL/g inpores with diameters of greater than 20 nm.
 6. The fluoridedsilica-coated alumina of claim 1, wherein: from 65 to 98% of surfacearea is in pores with diameters of greater than 6 nm; from 19.5 to 55%of surface area is in pores with diameters of greater than 10 nm; thefluorided silica-coated alumina has a surface area of from 250 to 475m²/g in pores with diameters of greater than 6 nm; and the fluoridedsilica-coated alumina has a surface area of from 78 to 200 m²/g in poreswith diameters of greater than 10 nm.
 7. A catalyst compositioncomprising a metallocene compound, the fluorided silica-coated aluminaof claim 1, and an optional co-catalyst.
 8. The catalyst composition ofclaim 7, wherein the catalyst composition comprises one metallocenecompound.
 9. The catalyst composition of claim 7, wherein the catalystcomposition comprises two or more metallocene compounds.
 10. An olefinpolymerization process, the process comprising contacting the catalystcomposition of claim 7 with an olefin monomer and an optional olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer.
 11. The process of claim 10,wherein: the catalyst composition is contacted with ethylene and anolefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixturethereof; and the polymerization reactor system comprises a loop slurryreactor, a fluidized bed reactor, a solution reactor, or a combinationthereof.
 12. A process to produce the fluorided silica-coated alumina ofclaim 1, the process comprising contacting a fluoriding agent with asilica-coated alumina to produce the fluorided silica-coated alumina,wherein the silica-coated alumina has: a bulk density from 0.15 to 0.37g/mL; a total pore volume from 1.1 to 2.5 mL/g; a BET surface area from250 to 600 m²/g; and an average pore diameter from 10 to 25 nm.
 13. Asupported metallocene catalyst comprising: a metallocene compound; and afluorided silica-coated alumina; wherein: an amount of the metallocenecompound adsorbed per gram of the fluorided silica-coated alumina is atleast 55 μmol/g; or a number of molecules of the metallocene compoundadsorbed per nm² of surface area of the fluorided silica-coated aluminais at least 0.1 molecules per nm²; or both.
 14. The catalyst of claim13, wherein: the amount of the metallocene compound adsorbed per gram ofthe fluorided silica-coated alumina is from 55 to 155 μmol/g; and thenumber of molecules of the metallocene compound adsorbed per nm² ofsurface area of the fluorided silica-coated alumina is from 0.1 to 0.3molecules per nm².
 15. The catalyst of claim 13, wherein the catalysthas: a bulk density from 0.15 to 0.37 g/mL; a total pore volume from0.85 to 2 mL/g; a BET surface area from 200 to 500 m²/g; and an averagepore diameter from 10 to 25 nm and/or from 80 to 99% of pore volume inpores with diameters of greater than 6 nm.
 16. An ethylene polymerhaving: a melt index (MI) in a range from 0.1 to 10 g/10 min; and adensity in a range from 0.91 to 0.96 g/cm³; wherein the ethylene polymercontains: from 70 to 270 ppm solid oxide; and from 2 to 18 ppm fluorine.17. The polymer of claim 16, wherein the ethylene polymer contains: from100 to 200 ppm solid oxide; and from 4 to 12 ppm fluorine.
 18. Thepolymer of claim 16, wherein the ethylene polymer further contains from0.5 to 5 ppm of zirconium and/or hafnium.
 19. The polymer of claim 16,wherein the ethylene polymer contains, independently, less than 0.1 ppmof Mg, V, Ti, and Cr.
 20. The polymer of claim 16, wherein the solidoxide contains silica and alumina at a weight ratio of silica:aluminafrom 20:80 to 60:40.
 21. The polymer of claim 16, wherein the ethylenepolymer comprises an ethylene homopolymer and/or an ethylene/α-olefincopolymer.
 22. An article of manufacture comprising the polymer of claim16.